WO2019117162A1 - Composé, générateur de base latent, composition de résine photosensible contenant ledit composé et produit durci - Google Patents

Composé, générateur de base latent, composition de résine photosensible contenant ledit composé et produit durci Download PDF

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Publication number
WO2019117162A1
WO2019117162A1 PCT/JP2018/045550 JP2018045550W WO2019117162A1 WO 2019117162 A1 WO2019117162 A1 WO 2019117162A1 JP 2018045550 W JP2018045550 W JP 2018045550W WO 2019117162 A1 WO2019117162 A1 WO 2019117162A1
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group
unsubstituted
carbon atoms
substituted
compound
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PCT/JP2018/045550
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English (en)
Japanese (ja)
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智幸 有吉
光裕 岡田
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株式会社Adeka
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Priority to KR1020207000839A priority Critical patent/KR102669269B1/ko
Priority to CN201880055088.3A priority patent/CN111417623A/zh
Priority to JP2019559669A priority patent/JP7314055B2/ja
Publication of WO2019117162A1 publication Critical patent/WO2019117162A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin

Definitions

  • the present invention relates to a novel compound useful as a polymerization initiator for use in a photosensitive resin composition, a latent base generator containing the compound, a photosensitive resin composition comprising the photosensitive resin and the compound, and The present invention relates to a cured product of the photosensitive resin composition.
  • a photosensitive resin composition is a photosensitive resin to which a photopolymerization initiator is added, and can be polymerized and cured or developed by energy beam (light) irradiation, so a photocurable ink, photosensitive printing It is used in printing plates, various photoresists, photocurable adhesives and the like.
  • the photopolymerization initiator is divided into a photo radical generator, a photo acid generator, and a photo base generator according to the difference in active species generated by energy beam (light) irradiation.
  • the photo radical generator has the advantage that the curing speed is fast and there is no remaining active species after curing, etc. However, since curing inhibition by oxygen occurs, it is necessary to provide an oxygen blocking layer etc. in curing the thin film. There is.
  • the photoacid generator has an advantage of not being inhibited by oxygen, but has disadvantages such as corrosion of the metal substrate due to the remaining of the acid of the active species and denaturation of the resin after curing.
  • Photo base generators have attracted attention because they are unlikely to cause the problems described above such as curing inhibition by oxygen and corrosion due to residual active species, but they generally have the problem of low sensitivity (low curability) compared to photo acid generators. .
  • the photo base generators are disclosed, for example, by Patent Documents 1 to 4.
  • the object of the present invention is to provide a novel compound which exhibits sufficient absorption to long wavelength ultraviolet light (particularly 365 nm) and has satisfactory sensitivity (base generation ability), latent base generator containing the compound,
  • the present invention is to provide a photosensitive resin composition containing the compound as a polymerization initiator and a cured product thereof.
  • the inventors conducted intensive studies and found that a compound having a specific structure has high sensitivity (base generation ability) as a polymerization initiator.
  • the present invention achieves the above object by providing the following [1] to [9].
  • R 1 represents a hydrogen atom, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms having an unsubstituted or substituted group
  • R 2 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a cyano group, a nitro group, -OR 8 , -COOR 8 , -CO-R 8 , -SR 8 , a halogen atom
  • R 3 represents an unsubstituted or substituted
  • At least one of R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the general formula (I) has a nitro group, a benzoyl group or an o-methylbenzoyl group as a substituent
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the above general formula (I) is a group represented by the following general formula (II) [1 ] Or the compound as described in [2].
  • R 25 , R 26 , R 27 , R 28 and R 29 are each independently a hydrogen atom, a cyano group, a nitro group, -OR 30 , -COOR 30 , -CO-R 30 , -SR 30
  • R 30 represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to
  • R 31 represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsubstituted or substituted aromatic 6 to 20 carbon atoms
  • X 2 is a group represented by —NR 32 R 33 , the following (a ′) or the following (b ′)
  • R 32 and R 33 each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms having an unsubstituted or substituted group 6 to 20 aromatic hydrocarbon groups
  • R 32 and R 33 are linked to each other to have a substituted or unsubstituted ring formed of a hydrogen atom, a nitrogen atom and a carbon atom, a ring having 1 to 20 carbon atoms, or an unsubstituted or substituted group and a hydrogen And forms a ring having 1 to 20 carbon atoms consisting of
  • R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R 43 each independently have a hydrogen atom or an unsubstituted or substituted group
  • at least one pair of R 34 and R 35 , R 36 and R 37 , R 38 and R 39 , R 40 and R 41 and R 42 and R 43 have each an unsubstituted or substituted group and A ring of 1 to 20 carbon atoms consisting of hydrogen, nitrogen and carbon, or a ring of 1 to 20 carbons containing unsubstituted or substituted and consisting of hydrogen, oxygen, nitrogen and carbon Form a * Represents a bond.
  • a latent base generator comprising the compound according to any one of [1] to [3].
  • the photosensitive resin composition containing the polymerization initiator (A) and photosensitive resin (B) as described in [6] [5].
  • cured material which has the process of irradiating an energy ray to the photosensitive resin composition as described in [9] [6] or [7].
  • the novel compound of the present invention is a carbamoyl oxime compound represented by the above general formula (I).
  • the carbamoyl oxime compound has a geometric isomer due to a double bond of oxime, but the above general formula (I) does not distinguish them.
  • the compound represented by the above general formula (I), the compound which is a preferable form of the compound described later, and the exemplified compound represent a mixture of geometric isomers or one of them, and a structure shown It is not limited to the isomer of When the methylene group in the group represented by R 1 to R 8 and R 11 to R 22 in the general formula (I) is substituted by a group containing a carbon atom, the number of carbon atoms thereof is included. Is the specified number of carbon atoms.
  • Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 and R 11 to R 22 in the general formula (I) include, for example, methyl, ethyl, propyl and isopropyl , Butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl Hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like.
  • the methylene group in these aliphatic hydrocarbon groups is —O—, —COO—, —OCO—, —CO—, —CS— or —S -, - SO -, - SO 2 -, - NR -, - NR-CO -, - CO-NR -, - NR-COO -, - there in OCO-NR- or -SiRR'- substituted radicals May be However, these substituted divalent groups are not adjacent to each other.
  • R and R ' are unsubstituted aliphatic hydrocarbon groups, and as the unsubstituted aliphatic hydrocarbon group, unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • R 1 to R 8 and R 11 to R 22 unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • R 1 to R 8 and R 11 to R 22 unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • the same groups as those exemplified as the aliphatic hydrocarbon group of the number 1 to 20 can be mentioned.
  • Examples of the unsubstituted C6-C20 aromatic hydrocarbon group represented by R 1 to R 8 and R 11 to R 22 in the general formula (I) include phenyl, naphthyl, phenanthryl, pyrenyl and biphenyl And phenyl substituted with an aliphatic hydrocarbon group, naphthyl, phenanthryl, pyrenyl and biphenyl and the like.
  • R 1 to R 8 and R 11 to R 22 each represent an alkylene moiety in these aromatic hydrocarbon groups or a methylene group at the bonding portion between an aromatic ring and an aliphatic hydrocarbon group is —O—, — COO -, - OCO -, - CO -, - CS -, - S -, - SO -, - SO 2 -, - NR -, - NR-CO -, - CO-NR -, - NR-COO-, It may be a group substituted with -OCO-NR- or -SiRR'-. However, these substituted divalent groups are not adjacent to each other.
  • Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above. It can be mentioned.
  • R and R ' are unsubstituted aliphatic hydrocarbon groups, and as the unsubstituted aliphatic hydrocarbon group, unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • the same groups as those exemplified as the aliphatic hydrocarbon group of the number 1 to 20 can be mentioned.
  • R 1 ⁇ R 8 Represented by R 1 ⁇ R 8, R 11 an aliphatic hydrocarbon group and R 1 of ⁇ R 22 at 1 to 20 carbon atoms having a substituent represented ⁇ R 8, R 11 ⁇ R 22
  • the hydrogen atom of the unsubstituted body demonstrated above is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro.
  • Those substituted with a group, a hydroxyl group, a thiol group, -COOH or -SO 2 H can be mentioned.
  • the ring composed of atoms include a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, an imidazoline group, a pyrazole group, a pyrazolidine group, a piperidine group, a piperazine group and the like as a group containing a nitrogen atom to be bound.
  • aliphatic hydrocarbon group examples include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above. It can be mentioned.
  • Examples of the ring composed of atoms and carbon atoms include morpholine group, oxazole group, oxazoline group, oxadiazole group and the like as a group including a nitrogen atom bonded thereto, and the hydrogen atom of these rings is a fluorine atom It may be substituted by a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO 2 H or an aliphatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above. It can be mentioned.
  • Examples of the unsubstituted heterocyclic group having 2 to 20 carbon atoms represented by R 2 to R 8 in the general formula (I) include a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group and a morpholine group.
  • the alkylene moiety in the group containing these heterocycles and the methylene group at the bonding part between the heterocycle and the alkyl group are —O—, —COO—, —OCO—, —CO -, - CS -, - S -, - SO -, - SO 2 -, - NR -, - NR-CO -, - CO-NR -, - NR-COO -, - OCO-NR- or -SiRR ' It may be a group substituted by-. However, these substituted divalent groups are not adjacent to each other.
  • aliphatic hydrocarbon group examples include those exemplified as the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above.
  • R and R ' are unsubstituted aliphatic hydrocarbon groups, and as the unsubstituted aliphatic hydrocarbon group, unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • R 1 to R 8 and R 11 to R 22 unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • R 1 to R 8 and R 11 to R 22 unsubstituted carbon atoms represented by R 1 to R 8 and R 11 to R 22 described above
  • the same groups as those exemplified as the aliphatic hydrocarbon group of the number 1 to 20 can be mentioned.
  • Examples of the group having a substituent having 2 to 20 carbon atoms and having a substituent represented by R 2 to R 8 include a hydrogen atom of a group containing the unsubstituted heterocycle described above, What is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO 2 H can be mentioned.
  • the group to be substituted contains a carbon atom or has a substituent, the number including the number of carbon atoms thereof is the specified number of carbon atoms.
  • the novel compound represented by the above general formula (I) is a group in which X 1 is a group represented by -NR 11 R 12 from the viewpoint of excellent UV sensitivity and curability.
  • a compound which forms a ring having 1 to 20 carbon atoms consisting of atoms and carbon atoms, or C 1 to C 1 consisting of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom, wherein R 11 and R 12 are mutually linked Compounds which form 20 rings are preferred.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is a nitro group or cyano from the viewpoint of excellent UV sensitivity and long wavelength absorption and solubility in resin.
  • Compounds which are a group, a hydroxyl group, a carboxyl group or a thiol group or a group having these groups as a substituent are preferable, and a compound having a nitro group or a group having a nitro group as a substituent is preferable More preferred is a compound in which R 3 is a group having a nitro group as a substituent.
  • a nitrophenyl group is preferable.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is a benzoyl group, an o-methyl benzoyl group or a trifluoromethyl group from the viewpoint of excellent sensitivity.
  • R 3 is a group or a group having these groups as a substituent are also preferable, and in particular, compounds in which R 3 has a benzoyl group as a substituent are preferable.
  • a benzoylphenyl group is preferable.
  • At least one of R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the general formula (I) has a nitro group, a benzoyl group or an o-methylbenzoyl group as a substituent It is preferable that the compound which is a group has a long absorption wavelength range (365 nm) and is used as a polymerization initiator since it is excellent in sensitivity.
  • R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms
  • R 2 , R 4 , R 5 , R 6 and R 7 are hydrogen atoms
  • X 1 is -NR 11 or group a
  • R 11 and R 12 represented by R 12 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or R 11 and R 12 combine with a hydrogen atom from one another, a nitrogen A ring of 1 to 20 carbon atoms consisting of atoms and carbon atoms or a ring of 1 to 20 carbon atoms consisting of hydrogen atom, oxygen atom, nitrogen atom and carbon atoms is formed
  • R 3 is a nitro group or The compound which is a group which has a benzoyl group as a substituent.
  • R 1 to R 8 and R 11 to R 22 an unsubstituted or substituted carbon atom having 6 to 6 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the above general formula (I) is a group represented by the above general formula (II), and the other is a hydrogen atom, no Compounds having a substituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 12 carbon atoms have high sensitivity. It is preferable from the point of being easy to manufacture.
  • the compound whose n in the said General formula (I) is 0 is preferable from being excellent in a sensitivity, when it uses as a polymerization initiator.
  • the compound whose n in the said General formula (I) is 1 is preferable from the hardened
  • a carbamoyl oxime compound of the present invention represented by the above general formula (I).
  • X 1 indicates a case of -NR 11 R 12, by changing the amine used, X 1 is represented by (a) or (b) Certain compounds can also be made.
  • the oxime compound and the carbamoyl oxime compound can also be produced by the method described in Japanese Patent No. 4223071.
  • X 1 is a group represented by said (a) or (b) by changing the amine to be used. Certain compounds can also be made.
  • the oxime compound and the carbamoyl oxime compound can also be produced by the method described in Japanese Patent No. 4223071.
  • the novel compound of the present invention can be suitably used as a polymerization initiator, which is a photo base generator described below, from the viewpoint of the excellent curability of the photosensitive resin and the high sensitivity to energy rays. It can be used as a mold resist or the like.
  • the latent base generator of the present invention contains at least one compound represented by the above general formula (I).
  • the content of the compound represented by the above general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.
  • the latent base generator generates a base by light or heat and can be used as a polymerization initiator, a base catalyst, or a pH adjuster.
  • a latent photobase generator which generates a base by irradiation with light is more preferable because of excellent operability.
  • the polymerization initiator (A) contains at least one compound represented by the above general formula (I).
  • the content of the compound represented by the above general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.
  • the content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the photosensitive resin (B). It is.
  • the content of the polymerization initiator (A) is 1 part by mass or more, curing defects due to insufficient sensitivity can be easily prevented, and it is preferable that the content is 20 parts by mass or less. Is preferable because it can suppress the
  • the photosensitive resin (B) used in the present invention is a resin whose curing temperature is lowered by using an anionically polymerizable functional group or a base as a catalyst, and a photosensitive resin which is polymerized and cured by irradiation with energy rays such as ultraviolet rays. Resin or a cured resin whose curing temperature is lowered.
  • the above-mentioned anionically polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by active energy rays such as ultraviolet light, and examples thereof include an epoxy group, an episulfide group, and a cyclic monomer ( ⁇ -valerolactone, ( ⁇ -caprolactam), catalysts for urethane bond formation with isocyanate and alcohol, catalysts for Michael addition of (meth) acrylic groups, catalysts for cross-linking reaction of silicone resin, and the like.
  • the photosensitive resin (B) include epoxy resin, phenol resin, polyamide resin, polyurethane resin, nylon resin, polyester resin, silicone resin and the like. These resins may be used alone or in combination of two or more. Among them, a combination of an epoxy resin and a phenol resin is preferable in terms of rapid reaction progress and good adhesion.
  • epoxy resin examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcine, pyrocatechol, phloroglucinol and the like; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (ortho cresol) , Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis (ortho cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4 -Bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobi Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sulfophenol, sulf
  • these epoxy resins may be those which are internally crosslinked by prepolymers of terminal isocyanates or those which are polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) .
  • a polyvalent active hydrogen compound polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.
  • those having a glycidyl group are preferable, and those having a glycidyl group having two or more functional groups are more preferable, from the viewpoint of excellent curability.
  • phenol resin As said phenol resin, the phenol resin which has a 2 or more hydroxyl group in 1 molecule is preferable, and a generally well-known thing can be used.
  • a phenol resin for example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac Type phenol resin, biphenylaralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenolaralkyl type phenol Resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, These include, but are not limited
  • polyamide resin as acid dianhydride, ethylene tetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride , 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride
  • diamine (o-, m- or p-) phenylenediamine, (3,3'- or 4,4'-) diaminodiphenyl ether, diamino benzophenone nonone, (3,3'- or 4,4'- And the like. Resins using diaminodiphenylmethane as a raw material can be mentioned.
  • polyurethane resin as a diisocyanate, a polyfunctional isocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and a polyol (polyfunctional alcohol) such as polyether polyol, polyester polyol, polycarbonate polyol etc. as raw materials Resin etc. are mentioned.
  • a resin using a cyclic monomer such as ⁇ -caprolactam and lauryl lactam as a raw material can be mentioned.
  • polyester resin a resin using a cyclic monomer such as ⁇ -valerolactone or ⁇ -propiolactone as a raw material can be mentioned.
  • silicone resin examples include methyl silicone resin, methyl / phenyl silicone resin, organic resin-modified silicone resin and the like.
  • additives such as an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer and a solvent can be used as an optional component.
  • the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper and the like can be mentioned.
  • metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina
  • layered clay minerals miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide
  • inorganic compounds are used, for example, as a filler, an antireflective agent, a conductive material, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink-emitting agent and the like.
  • color material examples include pigments, dyes, and natural dyes. These coloring materials can be used alone or in combination of two or more.
  • the pigment examples include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthrone compounds, perinones Compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, lake pigments, furnace method, channel method or thermal Carbon obtained by the above method, or carbon black such as acetylene black, ketjen black or lamp black; Those prepared or coated with epoxy resin, those obtained by dispersing the above carbon black in a resin solution in advance and adsorbing a resin of 20 to 200 mg / g, those obtained by
  • Graphite Graphitization Carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nano horn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese based, ferroci Chloride, phosphate blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, amber, etc.
  • Organic or inorganic pigments can be used. These pigments may be used alone or in combination of two or more.
  • pigments can also be used as the pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, Pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 9 , 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 137, 138, 139, 147, 148, 150, 151, 152,
  • the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes And dyes such as cyanine dyes, and the like, and these may be used as a mixture of two or more.
  • latent epoxy curing agent examples include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salt, imidazoles, guanamines, imidazoles, ureas, melamine and the like. It can be mentioned.
  • a sulfur atom-containing compound is generally used as the chain transfer agent or sensitizer.
  • a solvent capable of dissolving or dispersing the above-mentioned components for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl Ketones, ketones such as methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate Ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, tex
  • ketones or ether ester solvents in particular, propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone are preferably used from the viewpoint of alkali developability, patterning property, film forming property and solubility.
  • the content of the solvent is not particularly limited, and each component is uniformly dispersed or dissolved, and a liquid to paste form in which the photosensitive resin composition of the present invention is suitable for each use.
  • the amount of the solid content (all components other than the solvent) in the photosensitive resin composition of the present invention is preferably 10 to 90% by mass.
  • the photosensitive resin composition of this invention can also improve the characteristic of hardened
  • the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin and the like can be mentioned.
  • the amount thereof used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the photosensitive resin (B).
  • a surfactant a silane coupling agent, a melamine compound and the like can be further used in combination.
  • the surfactant examples include fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; and anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; Cationic surfactants such as amine halide salts and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as activators can be used, and these may be used in combination.
  • fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
  • anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates
  • silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, it has an isocyanate group such as KBE-9007, KBM-502, KBE-403, etc., methacryloyl group or epoxy group.
  • a silane coupling agent is preferably used.
  • Examples of the melamine compound (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, all or part of the (poly) active methylol groups of the nitrogen compound such as methylol urea (CH 2 OH groups)
  • the compound etc. by which (at least 2) was alkyl-etherified can be mentioned.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, which may be identical to or different from each other.
  • the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
  • hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
  • alkyl aleated melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable from the viewpoint of solubility in a solvent and difficulty in crystal precipitation from the photosensitive resin composition.
  • the amounts of the optional components other than the (A) polymerization initiator and the photosensitive resin (B) are the purpose of use.
  • the amount is appropriately selected and not particularly limited, but preferably 50 parts by mass or less in total with respect to 100 parts by mass of the photosensitive resin (B).
  • the photosensitive resin composition of the present invention can be cured by irradiation with energy rays.
  • the cured product is formed into an appropriate shape according to the application.
  • the photosensitive resin composition of the present invention can be formed by a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, etc. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like. In addition, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the method of application is not limited.
  • an ultra high pressure mercury lamp As a light source of energy rays used when curing the photosensitive resin composition of the present invention, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, carbon High energy energy such as electromagnetic wave energy, electron beam, X ray, radiation having wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source etc
  • a line can be used, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. which emit light with a wavelength of 300 to 450 nm are preferably used.
  • a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers It is also possible to use those emitting light in the visible to infrared region, such as various semiconductor lasers and YAG lasers. When using these laser beams, preferably, sensitizing dyes that absorb the relevant region of visible to infrared are added.
  • the photosensitive resin composition of the present invention it is usually necessary to heat after the irradiation of the energy beam, and heating at about 40 to 150 ° C. is preferable in view of the curing rate.
  • the photosensitive resin composition of the present invention is a photocurable coating or varnish; a photocurable adhesive; a coating agent for metals; a printed circuit board; a liquid crystal display of color display such as a color television, a PC monitor, a portable information terminal, a digital camera, etc.
  • the photosensitive resin composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for the purpose of forming a projection for a vertical alignment type liquid crystal display element.
  • it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertically aligned liquid crystal display devices.
  • the above-mentioned spacer for a liquid crystal display panel is (1) a step of forming a coating of the photosensitive resin composition of the present invention on a substrate, (2) energy rays through a mask having a predetermined pattern shape on the coating It is preferably formed by a step of irradiating (light), (3) a baking step after exposure, (4) a step of developing a film after exposure, and (5) a step of heating the film after development.
  • the photosensitive resin composition of the present invention to which a coloring material is added is suitably used as a resist constituting each pixel such as RGB in a color filter, or a black matrix resist forming a partition of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent is added, it is preferably used for an ink jet color filter partition having a profile angle of 50 ° or more.
  • the ink repellent agent a fluorine-based surfactant and a composition containing a fluorine-based surfactant are suitably used.
  • the partition formed from the photosensitive resin composition of the present invention divides the transferred body, and the drop is formed by the inkjet method in the recessed portion on the partitioned transfer body.
  • the optical element is manufactured by a method of applying to form an image area.
  • the said droplet contains a coloring agent and the said image area
  • the photosensitive resin composition of the present invention can also be used as a composition for a protective film or an insulating film.
  • it may contain an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, a mono- or difunctional (meth) acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or a silica sol.
  • the insulating film is used for the insulating resin layer in a laminate in which the insulating resin layer is provided on a peelable support base material, and the laminate is capable of developing with an alkaline aqueous solution, and the insulating resin layer
  • the film thickness is 10 to 100 ⁇ m.
  • the photosensitive resin composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound.
  • the photosensitive paste composition can be used to form fired product patterns such as partition patterns, dielectric patterns, electrode patterns and black matrix patterns of plasma display panels.
  • Step 2 In a 200-mL four-necked flask, 1.0 eq. , Aluminum chloride 2.5 eq. And dichloroethane (500% by weight of the theoretical yield) were added and stirring was carried out at 5 ° C. on an ice bath. There myristoyl chloride 1.3 eq. Was added dropwise. After the temperature was raised to room temperature, the mixture was stirred for 3 hours, 50 g of ion exchanged water was added, and the organic layer was separated. The organic layer was dried over anhydrous sodium sulfate, then the solvent was distilled off, ethanol was added and crystallization was performed.
  • Step 3 The crystals obtained by filtration were dried under reduced pressure at 50 ° C. to a constant weight to obtain ketone compound 1 in a yield of 65%.
  • Step 3 The ketone compound obtained in Step 2 was added to a 100 mL four-necked flask in 1.0 eq. , Hydroxylamine hydrochloride 2.0 eq. And pyridine (200% by weight of the theoretical yield) were added, and the mixture was heated and stirred at 95 ° C. for 2.5 hours under a nitrogen flow of 20 mL / min. After cooling to room temperature, 50 g of ion exchanged water was added to separate an organic layer. The organic layer was dried over anhydrous sodium sulfate, then the solvent was distilled off, and dried under reduced pressure at 50 ° C. to constant weight to obtain an oxime 1 in 88% yield.
  • Preparation Example 2 Synthesis of Oxime 2 The same procedure as Preparation Example 1 was carried out except that 4-fluoronitrobenzene in ⁇ Step 1> was changed to 4-fluorobenzophenone and myristoyl chloride in ⁇ Step 2> was changed to n-octanoyl chloride. The oxime compound 2 was obtained in a total yield of 11%.
  • Example 1 Compound No. 1 Synthesis of No. 1 Nitrogen flow in a 100 ml four-necked flask, and oxime compound 1 at 1.0 eq. , Dichloromethane (500% by weight of theoretical yield), triethylamine 2.0 eq. Was added and stirring was carried out at 5 ° C. on an ice bath. There, 4-nitrophenyl chloroformate 1.1 eq. Was dissolved in dichloromethane and added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. After cooling again to 5 ° C. on an ice bath, piperidine 1.1 eq. Was added dropwise. Stir at room temperature for 3 hours and evaporate the solvent under reduced pressure.
  • Example 2 Compound No. Synthesis of Compound No. 2 The procedure of Example 1 was repeated except that the oxime compound 1 described in Example 1 was changed to the oxime compound 2; 2 was obtained in 54% yield. The resulting solid was analyzed for TG-DTA (melting point / ° C.), 1 H-NMR. The results are shown in [Table 1] and [Table 2].
  • Preparation Example 3 Synthesis of Oxime 3 The same procedure as Preparation Example 1 was carried out except that 4-fluoronitrobenzene in ⁇ Step 1> was changed to 4-fluorobenzophenone and myristoyl chloride in ⁇ Step 2> was changed to n-octanoyl chloride. The ketone compound 2 was obtained.
  • ⁇ Step 3> In a 100 mL four-necked flask, 1.0 eq. , DMF (300% by weight of the theoretical yield), hydrochloric acid 1.2 eq. The mixture was added in the following order and stirred at 5 ° C. on an ice bath. There is isobutyl nitrite 1.2 eq. Was added dropwise.
  • the mixture was heated to room temperature and stirred for 6 hours. Thereafter, 50 g of ion exchange water and ethyl acetate were added to separate an organic layer. The organic layer was washed with water three times and concentrated under reduced pressure with an evaporator to obtain oxime 3. The obtained oxime body 3 was used for the next reaction without purification.
  • Example 3 Compound No. 3 Synthesis of 75 N2 was added to a 100 ml four-necked flask and the oxime 3 was treated with 1.0 eq. , Dichloromethane (500% by weight of theoretical yield), triethylamine 2.0 eq. Was added and stirring was carried out at 5 ° C. on an ice bath. There, 4-nitrophenyl chloroformate 1.1 eq. Was dissolved in dichloromethane and added dropwise. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. After cooling again to 5 ° C. on an ice bath, piperidine 1.1 eq. Was added dropwise. Stir at room temperature for 5 hours and evaporate the solvent under reduced pressure.
  • Example 4 Compound No. 4 Synthesis of Compound No. 76.
  • the procedure of Example 3 was repeated except that the piperidine described in Example 3 was changed to morpholine, and the compound No. 76 were obtained in a yield of 51%.
  • the resulting solid was analyzed for TG-DTA (melting point / ° C.), 1 H-NMR. The results are shown in [Table 1] and [Table 2].
  • Example 5 Compound No. 5 Synthesis of 77. Piperidine 1.1 eq. Described in Example 3 The piperazine 0.50 eq. The same procedures as in Example 3 were carried out except that the compound No. 1 was changed to 77 was obtained in 43% yield. The resulting solid was analyzed for TG-DTA (melting point / ° C.), 1 H-NMR. The results are shown in [Table 1] and [Table 2].
  • Example 6 Compound No. 6 Synthesis of Compound No. 152 The procedure of Example 3 was repeated except that the piperidine described in Example 3 was changed to dibutylamine, and the compound No. 152 was obtained in 38% yield. The resulting solid was analyzed for TG-DTA (melting point / ° C.), 1 H-NMR. The results are shown in [Table 1] and [Table 2].
  • Comparative Example 1 The following comparative compound Nos. 1 was used.
  • Evaluation Examples 1 to 5 and Comparative Evaluation Example 1 Evaluation of Optical Resolution Compound No. 1 1, No. 75, no. 76, no. 77, no. No. 152 and the following comparative compound Nos. 1 was adjusted to 1.0 ⁇ 10 ⁇ 4 mol of an acetonitrile solution and placed in a covered quartz cell.
  • the sample was irradiated with ultraviolet light from an ultrahigh pressure mercury lamp as a light source under the conditions of 100 mJ / cm 2 , 500 mJ / cm 2 and 1000 mJ / cm 2 (integrated light quantity at 365 nm) to investigate the degradability.
  • the amount of decomposition of the unirradiated peak as 0 using HPLC was expressed as%.
  • the novel compound of the present invention has high degradability to UV light, and therefore, the amount of base generated by decomposition is large, and the photosensitive resin composition cures with high sensitivity It shows the sex.
  • B-1 EPPN-201 Phhenolic novolac epoxy resin, epoxy equivalent 193 g / eq., Nippon Kayaku Co., Ltd.
  • C-1 FZ-2122 Polyether modified polysiloxane, manufactured by Toray Dow Corning
  • Photosensitive composition No. 1 to No. 6 and Comparative Photosensitive Composition No. 1 (applying amount about 2.0 cc) was coated on a glass substrate by a spin coater (500 rpm x 2 seconds ⁇ 1800 rpm x 15 seconds ⁇ slope x 5 seconds) and prebaked on a hot plate (90 ° C x x 120 seconds). Thereafter, ultraviolet light was divided and exposed (60, 120 mJ / cm 2 , gap: 20 ⁇ m, illuminance: 20.0 mW / cm 2 ) using a Topcon exposure machine. After exposure, post-baking was performed on a hot plate (120 ° C.
  • the photosensitive composition of the present invention exhibited a large line width (high sensitivity) and a high residual film ratio (high curability) as compared to the comparative photosensitive composition. From the above, it is clear that the compounds of the present invention are excellent as polymerization initiators.
  • Photosensitive composition No. 7 to No. 9 and Comparative Photosensitive Composition No. 2 and No. 3 (coating amount about 4.0 cc) was coated on a glass substrate by a spin coater (500 rpm x 2 seconds ⁇ 1800 rpm x 15 seconds ⁇ slope x 5 seconds) and prebaked on a hot plate (90 ° C x x 120 seconds). Thereafter, ultraviolet light was exposed using a Topcon exposure machine (1000 mJ / cm 2 , gap: 20 ⁇ m, illuminance: 20.0 mW / cm 2 ). After exposure, post-baking was performed on a hot plate (120 ° C. ⁇ 5 minutes).
  • the surface was rubbed with a cotton swab to check if a tack remains. Those with no tack remained were rated as ⁇ , and those with tack remaining as ⁇ .
  • Compounds having an evaluation of ⁇ are preferable as polymerization initiators because of their high curability.
  • the ultraviolet and visible absorption spectrum was measured using the spectrophotometer about the obtained sample, and the transmittance
  • Compounds having a transmittance of 80% or more are preferable as polymerization initiators because of high transparency, and compounds having a transmittance of less than 80% have low transparency as polymerization initiators for applications requiring transparency. Not desirable.
  • Spectrophotometer Hitachi High-Tech Spectrophotometer U-3900
  • the compound of the present invention is a polymerization initiator which is excellent in curability and transparency in a composition using a silicone resin.
  • Photosensitive composition No. 10 and No. 11 and Comparative Photosensitive Composition No. 1 4 (applying amount of about 4.0 cc) was coated on a glass substrate with a spin coater (500 rpm ⁇ 2 seconds ⁇ 1800 rpm ⁇ 15 seconds ⁇ slope ⁇ 5 seconds) and prebaked on a hot plate (90 ° C. ⁇ ) 120 seconds). Then, place the step tablet on the coated film, ultraviolet light using a LED exposure device (365 nm, 385 nm, 395 nm) was exposed (3000 mJ / cm 2, illuminance: 20.0mW / cm 2). After exposure, it was post-baked on a hot plate (100 ° C.
  • a photosensitive resin composition having 5 or more stages is preferable because of its excellent sensitivity, and those having 10 or more stages are particularly preferable.
  • the compound of the present invention is a polymerization initiator having excellent curability in a composition using an epoxy resin and a thiol as a curing agent.
  • Photosensitive composition No. 12 and No. 13 and Comparative Photosensitive Composition No. 5 (applying amount of about 4.0 cc) was coated on a glass substrate by a spin coater (500 rpm ⁇ 2 seconds ⁇ 1800 rpm ⁇ 15 seconds ⁇ slope ⁇ 5 seconds) and prebaked on a hot plate (100 ° C. ⁇ ) 10 minutes). Thereafter, ultraviolet light was divided and exposed (1000, 3000 mJ / cm 2 , gap: 20 ⁇ m, illuminance: 20.0 mW / cm 2 ) using a Topcon exposure machine. After exposure, post-baking was performed on a hot plate (100 ° C.
  • the compound of the present invention is a polymerization initiator having excellent curability in a resin composition using a polyamic acid.
  • the compounds of the present invention can also be used as thermal base generators.
  • Reference Example 1 The photosensitive composition No. 1 above.
  • the coating film was produced by the method similar to the above using 11. The coating was heated at 150 ° C. for 60 minutes using an oven. When the obtained film was developed with IPA, the residual film ratio was 40.5%, and it could be confirmed that the film was cured.
  • Reference Example 2 Heating and development were carried out in the same manner as in Reference Example 1 except that a composition to which A-1 (compound No. 1) was not added was used, but no film was left.
  • the compound of the present invention can also be used as a thermal base generator.
  • novel compound of the present invention when used as a polymerization initiator, can generate a base more efficiently than conventional photo base generators, so that the photosensitive resin can be cured even at a low exposure amount.

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Abstract

Le but de la présente invention est de fournir un nouveau composé présentant une absorption adéquate de lumière UV à grande longueur d'onde (en particulier 365 nm) et une sensibilité satisfaisante (capacité de génération de base), un générateur de base latent contenant ledit composé, une composition de résine photosensible contenant ledit composé en tant qu'initiateur de polymérisation, et un produit durci correspondant. La présente invention concerne un composé représenté par la formule générale (I). La présente invention concerne également un générateur de base latent contenant ledit composé, un initiateur de polymérisation comprenant ledit composé, une composition de résine photosensible contenant ledit initiateur (A) de polymérisation, une résine photosensible (B), un produit durci correspondant et un procédé de production associé. (Dans la formule, les symboles sont tels que définis dans la description.)
PCT/JP2018/045550 2017-12-13 2018-12-11 Composé, générateur de base latent, composition de résine photosensible contenant ledit composé et produit durci WO2019117162A1 (fr)

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KR1020207000839A KR102669269B1 (ko) 2017-12-13 2018-12-11 화합물, 잠재성 염기 발생제, 상기 화합물을 함유하는 감광성 수지 조성물, 및 경화물
CN201880055088.3A CN111417623A (zh) 2017-12-13 2018-12-11 化合物、潜伏性碱产生剂、含该化合物的感光性树脂组合物及固化物
JP2019559669A JP7314055B2 (ja) 2017-12-13 2018-12-11 化合物、潜在性塩基発生剤、該化合物を含有する感光性樹脂組成物、及び硬化物

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JP2020139136A (ja) * 2018-11-30 2020-09-03 株式会社Adeka 組成物、硬化物及び硬化物の製造方法
WO2020209205A1 (fr) * 2019-04-08 2020-10-15 株式会社Adeka Composé de carbamoyloxime, et initiateur de polymérisation et composition polymérisable contenant ledit composé
WO2020241529A1 (fr) * 2019-05-24 2020-12-03 株式会社Adeka Composé de carbamoyl-oxime, initiateur de polymérisation, et composition polymérisable contenant ledit composé
WO2021049489A1 (fr) * 2019-09-10 2021-03-18 株式会社Adeka Composé, agent de génération d'acide, composition, produit durci, motif et procédés de production de produit durci et de motif
JP2021066807A (ja) * 2019-10-23 2021-04-30 株式会社Adeka 重合性組成物、レジスト用重合性組成物及び硬化物

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